The TiO2 thin film, Ag NP and three Ag-NP/TiO2 composite thin films (COMP-Agn; n = 20, 50, and 75 Ag mol%) were successfully fabricated on quartz glass. The optical properties of the composite electrodes were investigated, and the results indicate a surface plasmonic resonance peak at 410 nm while the electrical resistivity of the composite thin films improved up to 6.9 × 10−5 Ω cm. The photo-response threshold of the Ag-NP/TiO2 composite thin films was enhanced and shifted into the visible and near-infrared when the chlorophyll dye was adsorbed onto them. The hall effect was performed on the fabricated thin films and the charge carrier concentrate value confirmed that the Ag/TiO2 with Ag concentrate >45% are found to be p-type. The n-types were observed till the Ag content in TiO2 was increased up to 45 mol%. COMP-Ag75 has a charge carrier concentration of 1.3 × 10−19 cm−3 as a p-type electrode was then employed to construct a p-DSSC. Such enhancement on photovoltaic activity can be attributed to the generated Z-scheme system in the anatase/rutile phase-junction Ag/TiO2 photocathode enhances the separation, diffusion, and transformation of electron/hole pairs inside the structure. This p-DSSC exhibits a photon-electrical conversion efficiency (PCE) of 0.37%. The PCE recorded is equal to or greater than those of traditional high-efficiency n-DSSCs. This allows the creation of a new generation of photocathodic p-DSSCs with previously unheard-of unprecedentedly high concentrations of Ag (up to 80 mol%) evenly scattered in a TiO2 matrix, and this efficacy is the highest ever reported for a p-type working Ag/TiO2/chlorophyll/iodine electrode. This may enable the use of this electrode as a component of photosensitizer tandem devices.